Oxypropylated derivatives of substituted phenol-sulfonic acid salts and method of making same



OXYPROPYLATED DERIVATIVES structure:

F SUBSTI- TUTED PHENOL-SULFONIC ACID SALTS AND METHOD OF MAKING SAME Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware No Drawing. Application June 8, 1953 Serial No. 360,371

Claims. to]. 260-512) This application is a continuation in part of my three copending applications,,SerialNumbers 164,856, 164,857, and 164,860, all filed May 27, 1950, all now abandoned.

The first aforementioned copending application is concerned with a sulfonic acid salt of the following structure:

in which the occurrences of R have their previous signifi- 'cance,'shall be xylene-insoluble; and the corresponding sodium salt owtmonn in which the occurrences of R and n have their previous significance and n has the identical value, as previously, shall be xylene-soluble. j r

The second aforementioned copending application is concerned with a sulfonic acid salt of the following oiolntom in which R is selected from the class of hydrocarbon substituents and hydrogen atoms, with'the proviso that there must be at least one hydrocarbon substituent and that the total number of carbon atoms substituted in the phenolic ring be not less than 12 and not over 35, and with the proviso that n be not less than 10 and not more than 50; and with the further proviso. that the corresponding sodium salt som United, States Patent 2,828,334 Patented Mar. 25, 1958 in which the occurrences of .R have their previous sig- :nificance, shall be insoluble in a mixture of two-thirds non-aromatic kerosene and one-third Xylene; and the corresponding sodium salt in which the occurrences of R and n have their previous significance and n has the identical value as previously, shall be soluble in a mixture consisting of two-thirds non-aromatic kerosene and one-third Xylene.

The third aforementioned copendin-g application is concerned with a sulfonicv acid salt of the following composition':.

econom st in which R represents an alkyl radical having at least 4 carbon atoms, and n and n represent a'numeral varying from 0 to 3, and n' represents a numeral varying from 50 to with the proviso that there must be at least 2 alkyl substituents in the molecule a'ndat least .2 sulfonic acid groups in the molecu-le;. and with the further proviso that the corresponding sodium salt ofthe following formula in which'all the characters have their previous significance (a), "(semen be soluble in water and in xylene but-insoluble .iha mixture of two-thirds non-aromatic kerosene and one= 'third xylene; and with the final proviso 'thats'aid aforementioned oxypropy-lated derivative be substantially insoluble in water and soluble in a mixtur'e of two=thifds non-aromatic kerosene and one-third xylene.

Thus, one aspect of the present invention is concerned with a water insoluble salt of the following composition: I I

in which R is an aromaticnndeus; R is a hydrocarbon substituent having not over 22 carbon atoms with the provisothat the combined radical (-R'),,R eon not over 2 aromatic rings; R 0 is an alkylenoxy' radical derived from a member of the class con isting of'etliylene: oxide, glycide, and methyl glycide; R 0 is a member of the class of alkylenoxy radicals derived from a member 'of the class'consisting of propylene oxide and butylene oxide; m is a numeral from 1 to 2; n is a numeral from 1 to 4; n is a numeral from O to 5; n" is a numeral from 0 to l; n' is a numeral from to 60; 11"" is a numeral from 1 to 6 but not greater than .the valence equivalency of the cation; said salt being a salt of the acid in which the characters have their previous significance; said acid being characterized by the fact that the sodium salt of the precursory acid of the following structure in which the characters have their previous significance,

is water soluble and surface active in an aqueous system; furthermore, the derivative salt in which the characters have their previous significance, is water soluble and surface'active in an aqueous system; additionally, the derivative salt in which the characters have their prior significance, n' being 15 to 60, is water insoluble and not surface active in an aqueous system.

It has been found that certain phenol-sulfonic acid salts, when subjected to oxyalkylation with an alkylene oxide having at least three and not over four carbon atoms (propylene oxide, butylene oxide, or a mixture of the two), yields a variety of valuable reaction products.

Generally, the present invention is concerned with oxypropylated or oxybutylated derivatives of certain substituted phenol sulfonic acids and their salts and the method of making the same.

The phenol-sulfonic acid salts employed as initial raw materials are characterized by the fact that as such they must be water-soluble and surface-active. Furthermore, they must be characterized by the fact that, if the phenolic hydroxyl is replaced by the radical O(R O) H in which R represents the radical derived from propylene oxide or butylene oxide, such products still be water soluble; whereas if the value 2 indicated immediately preceding is raised to a higher value, for instance, 15 to up to 40 or 60, the products are no longer water-soluble but become soluble in various non-aqueous solvents and particularly hydrocarbon solvents free. from an oxygen atom such as aromatic hydrocarbon solvents, aliphatic hydro rbon solvents, and the like." v t j The phenols which may be used to produce the initial compounds or ill 4 raw materials of sulfonic salts may have either one or two nuclei. Common examples are the following:

(R) SQLX SOLX in which X represents sodium, potassium or any cation which, in numerous cases, is"non-oxyalkylation-susceptible. Asis pointed out subsequently in the text, where the'invention is described with greater detail, one may have cations which presumably are oxyalkylation-susceptible such as monoethanol-amine, diethanolamine, triethanolamine, etc. Such cations may be present prior to oxypropylation or oxybutylation provided certain limitations are met or such cation may be introduced afterwards by liberating the free acid and then neutralizing with the selected amine. In the above formula, for the sake of simplicity, as a rule there is only one substituent radical shown in each nuclei. Obviously there may be more than one as, for example, sulfonic acids obtained from diamyl phenol, dinonylphenol, dodecyl phenol, etc. Other comparable phenol-sulfonic acids are the following, which may or may not have additional substituents:

SOaX

Other phenols which may be used are the following:

HOOQOH Gag It is to be noted in the ltteriithat the element sulfur appears in the compounds; other than in the sulfonic 7 acid radical,

5 V As to the manufacture of suchphenol-sulfohie acids, reference is made to the following patents:

U. 8. Patent No. I

One class of phenol-sulfonic acid salts included among those above described may be indicated thus sol-X p in which R is a substituent in an aromatic nucleus, R

is the phenolic nucleus which has not over 2 aromatic rings, n is a small whole number not over 3 and n is a small whole number not over 2, and X is the cation. It

has been previously pointed out that compounds of the above described must be water soluble and surface active. In some instances the surface activity and the water solubility can. be increased by reaction with a modest amount of alkylene oxide such as ethylene oxide, glycide,

or methyl glycide which increases certain hydrophile characteristics particularly when R is comparatively large, for instance, 12 to 18 carbon atoms and n' represents 2 or 3. Under such circumstances a derivative obtained, for example, by oxyalkylation with 1, 2, 3, 4, or molesof ethylene oxide, may greatly enhance the initial surface 1 activity of the compound in water and yield a more valuable compound when such hydrophile effect iseounterbalanced or offset.

Such compounds may be indicated thus:

in which R 0 is the alkylene oxide radical derived from ethylene oxide, glycide, or methyl glycide and n is the numeral 1 to Sand n has its previous significance.

In any event, the present invention is concerned with water-soluble substituted phenol-sulfonic acid salts or their oxyalkylated derivatives as described with the proviso, (a) that the compounds as such be water-soluble and, (b) furthermore, that when treated with one'or two moles of'propylene oxide or butylene oxide that the product must still be water soluble and surface active. In other words, the corresponding derivatives in which one or two moles of propylene oxide or butylene oxide enter into the structure of the compound must still be water-soluble and surface-active. Such compounds are designated as and Y (R2)[O (R3o),,"(R1o) E1 SOs-X Since the bulk of such sulfonic acid salts are derived from monohydric phenols the presentation is simplified by considen'ng such lirnited aspect in which the structure of the compound appears as follows: r j

6 R(R2)0(Rs0) 1 )n'H Oa-X i There is, however, a further proviso that inthe previous formulas when n is replaced by m with the proviso that m be a whole number from 15 to the structures'are'indicated thus uuno amo mam.

.SQs-X and,

(ammotm'omtalomiu sot-X t antaaomtmmn SOa'X I antnoomaonmalmmn SOs-X and such products mustbe water-insolubleand must be soluble in a non-oxygenated hydrocarbon solvent. 1

Actually, as illustrated by'certain subsequent examples, there may be more than one sulfonic acid'group present and thus the prior formulas may be rewritten to'take cognizance of this fact, thus,

specified can be prepared employing conventional procedure and particularly procedures described in the aforementioned list of patents concerned with the manufacture of such salts. If desired, there are some surface active salts available in the open market whichmay be obtained in the form of dry salts. They include, among others, monobutyl diphenyl sodium monosulfonate. At one time there was, and perhaps still is, on sale in the open market a compound'of the kind described as Example 5 in U. S. Patent 2,166,368, dated July 18, 1 939, to Flett.

As previously pointed out, the salt can be subjected to reaction with amodest amount of alkylene oxides, which introduce a predominantly hydrophile effect, such' as ethylene oxide, glycide and methyl glycide. On the other hand, in most instances the initial step is oxypropylation or oxybutylation for the obvious reason that the selected salt requires no further preliminary reaction Oxypropylation' or oxybutylation can be'conduc'ted any suitable means". One procedure, as described in the aforementioned copending applications, is simply to grind the powder to' a very fine state, for instance, to 200 mesh; suspend in an inert solvent along with an added catalyst such as finely powdered caustic soda or sodium methylate, and subject it to the reaction with propylene oxide, butylene oxide, or a mixture of the two. The second procedure involves the use of propylene carbonate or butylene carbonate for the reason that the carbonate eliminates the-use of a solvent or, rather, suspending agent; such carbonate acts both as a solvent and an oxyalkylatingagent and permits the reduction of a solid to a liquid which can be dispersed more readily in xylene than a solid even though still solvent-insoluble. No'

7 novelty is claimed to this step as such, i. e., the use of such alkylene carbonates, and as a matter of fact they can be used for the initial step, i. e., involving ethylene carbonate if such initial step precedes oxypropylation or oxybutylation. Such procedure has been used in connection with a wide variety of other products. For purpose of convenience, the manufacture of compounds using both procedures will be illustrated by Examples 1 to 38.

Oxypropylation r oxybutylation may be conducted intermittently or continuously until the appropriate point is reached. Intermittent oxypropylation or oxybutylation is particularly valuable for exploratory purposes, such as a routine test to determine the approximate degree of oxypropylation or oxybutylation required to convert a water soluble sulfonate of the kind specified into a water insoluble sulfonate which is usually soluble in xylene or in a mixture of xylene and kerosene or, for that matter, in kerosene alone. The equipment suitable for continuous oxypropylation or oxybutylation obviously may be em ployed in intermittent use. For convenience, reference hereafter will be principally to oxypropylation but obviously this applies also to oxybutylation.

In the particular procedure employed for preparation of the oxypropylated derivatives herein described. the autoclave was of conventional design. It was madeof stainless steel and had a capacity of approximately one gallon and a working pressure of one thousand pounds gauge pressure. The autoclave was equipped with the conventional devices and openings, such as the variable stirrer operating at speeds from 50 R. P. M. to 500 R. P. M., thermometer well and thermocouple for mechanical thermometer, emptying outlet; pressure gauge, manual vent line; charge hole for initial reactants; at least one connection for conducting the incoming alkylene oxide, such as ethylene oxide or propylene oxide, to the 7 bottom of the autoclave; along with suitable devices for both cooling and heating the autoclave, such as a cooling jacket, and preferably, coils in addition thereto, with the jacket so arranged that it is suitable for heating with steam or cooling with water, and further equipped with electrical heating devices. Such autoclaves are, of course, in essence, small scale replicas of the usual conventional autoclave used in oxyalkylation procedures.

Continuous operation. or substantially continuous'operation, is achieved by the use of a separate container to hold the alkylene oxide being employed, such as propylene oxide in the instant procedure. The container consists essentially of a laboratory bomb having a capacity of about one-half gallon, or somewhat in excess thereof. This bomb was equipped, also, with an inlet for charging, and

an outlet tube going to the bottom of the container, so as to permit dischar ing of alkylene oxide in the liquid phase to the autoclave. Other conventional equipment consists. of course. of the rupture disc. pressure gauge, sight feed glass. thermometer connection for nitrogen for pressurin bomb. etc. The bomb was placed on a scale during use and the connections between the bomb and the autoclave were flexible stainless steel hose or tubing. so that continuous weighings could be made without breaking or making any connections. This also applied to the nitrogen line, which was used to pressure the bomb reservoir. To the extent that it was required, any other usual conventional procedure or addition which provided greater safety was used, of course, such as safety glass, protective screens, etc.

In the following examples there are illustrated both intermediate and continuous oxypropylation, for the reason that intermediate oxypropylation is a convenient procedure by which exploratory oxypropylations can be made so as to determine initial xylene-solubility. Solubility in xylene, of course, remains as further oxypropylation proceeds and solubility and hydrophobe characteristics ma'yincrease to the degree that the product is soluble in solvents, such as a kerosene of little or no aromaticity. A

,At this point it may be well to point out that the butylene oxide available appears to be a mixture of the three isomers and for all practical purposes reacts as propylene oxide except that the speed of reaction is much slower. In other words, more time, higher temperature, greater pressure and perhaps an increased amount of catalyst may be required.

I have found that it is possible to conduct oxybutylation, particularly in the earlier stages, without too much difliculty although exhaustive oxybutylation may sometimes involve a time factor equal to that comparable to that of oxypropylation. Oxybutylations have been described in the literature comparable to that in connection with oxyethylation or oxypropylation.

Example 1 Grams Monobutyl phenyl-phenol sodium monosulfonate 600 Xylene 600 Sodium mcthylate 5 Propylene oxide 364 The powdered sulfonate was placed in the autoclave with 600 grams of xylene and 5 grams of sodium methylate, as indicated. The autoclave was then swept out with nitrogen and sealed. Stirring was started and then heat applied. The temperature was allowed to rise to approximately C. At this point propylene oxide was added to the extent of 364. grams. Notwithstanding the presence of the free hydroxyl radical, oxypropylation took place at a very slow rate. The time required to combine the propylene oxide was 10 hours. The maximum temperature of operation was C. Most of the time the temperature did not drop much below 170 C. The maximum pressure was 160 pounds per square inch. The product at this stage on a xylene-free basis calculated as follows:

- Percent Sulfonate 62.4 Propylene oxide 37.6

and on a xylene-containing basis calculated as follows:

Example 2 The autoclave was drained so as to permit 812 grams of the reaction mixture to stay in the autoclave. This was equivalent to 312 grams of the sulfonate, 188 grams of propylene oxide, and 312 grams of xylene. The sodium methylate previously added was ignored for purpose of calculation. 2 /2 grams of sodium methylate were added to the mixture and the autoclave flushed outwith nitrogen, as before, and oxypropylation resumed. 290 grams of propylene oxide were added during this step. The time required was 3 hours, with a maximum temperature of 175 C., and a maximum pressure of 180 pounds per square inch. The composition corresponded to the following, on a xylene-free basis:

Percent Sulfonate 39.4 Propylene oxide 60.6

On a xylene-containing basis it was calculated as follows:

Percent Sulfonate 28.3 Propylene oxide 43.4 Xylene 28.3

Example 3 Percent Sulfouate 24.4 Propylene oxide 75.6

On a xylene-containing basis it was calculated as follows:

. Percent Sulfonate 19.6 Propylene oxide 60.8 Xylene 19.6

This particular product was xylene-soluble, whereas, the intermediate products were merely dispersible when subjected to mechanical agitation. When xylene was evaporated from the mixture, it was a sticky, ambercolored, very viscous liquid. Needless to say, this product dissolved in xylene and other comparable aromatic solvents. It was not soluble in non-aromatic kerosene. It was somewhat water-emulsifiable, but not nearly as watersoluble as the original sulfonate. Possibly a very small portion was water-soluble, but the large percentage- 90% or morewas water-insoluble. It proved to be a particularly valuable coupling agent in the preparation of emulsions, where the emulsifying agent itself was the original sulfonate, or monobutyl diphenyl sodium monosulfonate. It was soluble to the extent of 1% or 2% in some typical lubricating oils which contained approximately 10% to 15% of additives, the bulk of which additives were alkaline earth soaps, mahogany sulfonates, or similar materials. If propylene oxide is replaced by butylene oxide, in either weight or molar ratio, the products are completely water-insoluble. The same can be accomplished by a 50:50 mixture of the two oxides.

Example 4 Grams Monobutyl phenyl-phenol sodium monosulfonate- 600 Xylene 600 Sodium methylate 10 Propylene oxide 1,800

Example. 5

The same procedure was followed, but using monoamylphenylphenol sodium sulfonate and employing the same procedure as in Example 4, immediately preceding.

. mp e 6 The same procedure was followed, but using monohexylphenylphenol sodium sulfonate and employing the same-procedure as in Example 4, preceding.

Example 7 The same procedure was followed, but using diamylphenylphenol sodium sulfonate and employing the same procedure as in Example 4, preceding.

Example 8 Examples 4 to 7 were repeated but: the amount of sulfonate employed in each instance was 500 grams in- 4 stead of 600 grams. The amount of sodium methylate,

employed was reduced from 10 grams to 9 grams. The amount of xylene employed was the same as previously.

Example 9 The same procedure was followed as in Examples 4 to 8, inclusive, except that the amount of sulfonate employed was reduced to 450 grams and the amount of sodium methylate reduced to 8 grams. In all other respects the oxypropylation procedure was the same as previously described. In any of these examples, or similar examples, invariably water insolubility increases, i. e., the products become less soluble in water, and hydrocarbon solubility increases. This is particularly true in respect to non-aromatic kerosene and especially butylene oxide if it is used, at least in part or entirely, to replace propylene oxide.

The xylene, which is used as a suspending agent in the above experiments, can be replaced by any other suitable non-reactive solvent, such as mesitylene, cymene, decalin, or the like. Xylene has the advantage of being cheap, readily available, and can be removed from the finished product by distillation, and particularly vacuum distillation. The use of such solvent, or, rather, suspending agent, at least in the initial stage, and particularly xylene, has the added advantage insofar that it practically indicates the end point, or, at least, the initial end point, i. e., the degree of oxypropylation or oxybutylation where the product is xylene-soluble. If batchwise oxypropylation or oxybutylation is being employed, or if continuous oxypropylation or oxybutylation is being employed and one takes samples intermittently, obviously mere casual examination indicates when the xylenecontaining mixture is homogenous, and usually, this also applies for a more dilute sample. In other words, the finished sample can then be diluted so as to contain 5% or less of the oxypropylation product, or oxybutylation product, and the remainder xylene. When such point is reached, at least the stage of initial xylene-solubility has been determined. Sometimes samples exhibit xylenesolubility in concentrated solutions, but require further oxypropylation or oxybutylation to make them xylenesoluble in dilute solutions, for instance, 2% to 5% of the oxyalkylation derivative. Solution in a non-aromatic hydrocarbon may require at least partial use of butylene oxide.

Example 10 Grams Phenol monosulfonate sodium salt produced in the manner described in Example 5 of aforemen- The powdered sulfonate was placed in an autoclave with 300 grams of xylene and 6 grams of sodium methylate, as indicated. The autoclave was then swept out with nitrogen and sealed. Stirring was started and then heat applied. The temperature was allowed to rise to approximately 175 C. At this point propylene oxide was added to the extent of 300 grams. Notwithstanding the presence of the free hydroxyl radical, oxypropylation took place rather slowly. The time required to combine the propylene oxide was 3% hours. At no time did the temperature go above the initial temperature of 175 C. Likewise, the temperature did not drop much below C. at any time. The maximum pressure was- Percent Sulfonate 50.0

Propylene oxide" 50.0

On a xylene-containing basis it calculated as follows:

Percent Sulfonate 33.3 Propylene oxide 33.3 Xylene 33.4

An examination of this product, both on a xylene-containing basis and after evaporation of xylene, did not show any marked change in solubility, although waterso'lubility apparently was decreased to at least some degree.

Example 11 Percent Su'lfonate 33.3 Propylene oxide 67.0

On a xylene-containing basis, it was calculated as follows:

Percent Sulfonate 25 Xylene 25 Propylene oxide 50 At the end of the second addition of propylene oxide the product showed solubility in a mixture of 65% xylene and 35% non-aromatic kerosene. The product, even when the xylene had been evaporated, showed less solubility in water than in the instance of Example 10, preceding. There was an unquestionable reduction on hydrophile character and an increase in hydrophobe character.

Example 12 A third portion of propylene oxide (300 grams) was added as before, after the autoclave had been opened and 7 grams of sodium methylate added. After the addition of methylate the autoclave was swept out with nitrogen gas as before; otherwise, the procedure, as far as temperature and pressure were concerned, was the same as in Examples and 11, preceding, i. e., the temperature range was within the limit of 167 C. to 180 C., and the pressure varied from 170 to 187 pounds per square inch. The time required was less than previously, apparently due to the addition of sodium methylate, and was 2 /2 hours. At the end of this time a sample showed a continued change in solubility character, i. e., it seemed to be even less water-soluble or dispersible than before, but was soluble in a mixture of 50% xylene and 50% non-aromatic kerosene. The product itself, on a xylenefree basis, represented 25% sulfonate and 75% propylene oxide. On a xylene-containing basis it represented sulfonate, 20% xylene and 50% propylene oxide.

Example 13 A final and last addition of propylene oxide was made to the above reaction mass. The amount added was 300 grams. No more catalyst was added. The temperature and pressure range were within the same limits, as in Example 12, preceding. The time required, how ever, was somewhat longer, i. e., 3% hours. The product, on a xylene-free basis, was water-dispersible and did not show much difference in this property compared with the previous sample. However, it was soluble in a mixture of 65 parts of non-aromatic kerosene and 35 parts of xylene and practically dissolved in a mixture of 75 non-aromatic kerosene and xylene. The

12 product, when free from xylene, was a thick, viscous, amber-colored liquid.

Calculated on a xylene-free basis, the product represented 20% sulfonate and propylene oxide. On a xylene-containing basis, it represented 16.6% sulfonate, 66.8% propylene oxide, and 16.6% xylene.

In the above calculation and in previous calculations, no cognizance was taken of the presence of sodium methylate, except as far as weight percentages were concerned, and no cognizance was taken of the fact, that small samples of 2 or 3 grams were taken out at the end of intermediate oxypropylations for examination.

Needless to say, this product dissolves in xylene and other comparable aromatic solvents. It proved to be a particularly valuable coupling agent in the preparation of emulsions where the emulsifying agent was the original sulfonate itself. It was soluble to the extent of 1% or 2%, and probably to a greater degree in some typical lubricating oils which contained approximately 10% to 15% of additives. The bulk of these additives were alkaline earth soaps, mahogany sulfonates, or similar materials. When butylene oxide replaced propylene oxide (gram for gram) the product became water-insoluble at an earlier stage. This final product then was soluble in 50:50 mixture of xylene and non-aromatic kerosene.

The procedure followed was the same as in Example 10, preceding, except that oxypropylation Was a continuous process involving a single step. The time required was somewhat less than in the interrupted procedures, being a total of 11%. hours. The maximum temperature employed was 178 C., and the maximum pressure was 205 pounds per square inch. The final product was comparable in every respect to the one described as the end product in Example 13, preceding. Replacing 1200 grams of propylene oxide by 1650 grams of butylene oxide gave a product completely soluble in non-aromatic kerosene.

Example 15 Grams Sulfonate as described in Example 4 of aforementioned U. S. Patent 2,166,136 300 Xylene 300 Sodium methylate 10 Propylene oxide 1,200

The procedure followed was the same as that described in Example 14, preceding, and the solubility characteristics of the final product were substantially the same as in the preceding example.

Example 16 Grams Sulfonate as described in Example 6 of aforementioned U. S. Patent 2,166,136 300 Xylene 300 Sodium methylate l0 Propylene oxide 1,200

mentioned U. S. Patent 2,223,363 300 Xylene 300 Sodium methylate 10 Propylene oxide 1,200

'"13 Theprocedure followedwas thesame as that described inExample 14, preceding, and the, solubility characteristics of the final product were substantially the same asfin the'preceding example.

of a polysulfonate 300 Xylene 300 Sodium methylate Pro ylene oxide 1,200

The procedure followed was the same as that described in Example 14,' preceding, and the solubility characteristics of the final product were substantially the same aslin the preceding example.

' The product above described is essentially a polyv butylated phenyl phenol mono-sulfonic acid sodium salt.

Equally satisfactory are polyamylated phenyl phenol monosulfonic acid sodium salt, or polyhexylated phenyl phenol monosulfonic acid sodium salt. Similarly, one may employ a polyoctylated 'phenyl phenol monosulfonic acid sodiuin salt, or the polydecylated phenyl phenol monestilfonic acid sodium salt.

Example 19 U V Grams Tributylated phenylphenol disulfonic acid sodium salt 300 Xylene 300 Sodium 'methylate 6 Propylene oxide; 3:00

The powdered sulfonate was placed in the autoclave with 300 grams of xylene and 6 grams of sodium methylate, as indicated. The autoclave was then swept out with nitrogen and sealed. Stirring was started and heat applied. The temperature was allowed to rise to 185 C. At this point propylene oxide was added to the extent of 300 grams. Notwithstanding the presence of the free hydroxyl radical, oxypropylation took place rather slow.- 1y. The time required to combine the propylene oxide was 6% hours. 7 At no time did the temperature go above 185 C. Likewise, the temperature did not drop below 168 C. at any time. i The maximum operating pressure was 178 pounds per square inch. The product at this stage, on a xylene-free basis, calculated as follows:

Percent Sulfonate 5 0.0 Propylene-oxide 50.0

On an xylene-containing basis, it calculated'as follows:

Percent Sulfonate 33.3 Propylene oxide 33.3 Xylene 33.4

An-examination of this product, both on a xyleneco ntaining basis and after evaporation of xylene, did not show any marked change in solubility, although watersolubility apparently was decreased to at least some degree.

Example, 20

conditions as previously, i. e., a temperature range of 14 171 C. to 183 C., and a maximum pressure of pounds ,per square inch. The composition, on a xylenefree basis, was as follows:

7 Percent 'Sulfonate '33 Propylene oxide 67.0 On a xylene-containing basis it was calculated as follows:

7 Percent Sulfonate 25 Xylene 25 Propylene oxide 50 At the end of the second addition of propylene oxide, the product showed solubility in a mixture of 65% xylene and 33% non-aromatic kerosene. The product, even when the xylene had been evaporated, showed less solubility in water. than in the instance of Example 19, preceding. There was an unquestionable reduction in hydrophile character and an increase in hydrophobe character.

Example 21 A third portion of propylene oxide (300 grams) was added as before; after the autoclave had been opened 8 grams of sodium methylate were added. After the addition of the methylate, the autoclave was, swept out with nitrogen gas as before. Otherwise, the procedure, as far as temperature and pressure were concerned, was the same asin Example 19, preceding, i. e., the temperature range was within the limit of 175 C. to 186 C., and the pressure varied from 169 to pounds per square inch. The time required was less than previously, apparently due to the added catalyst, and was slightly less than 6 /2 hours. At the end of this time a sample showed a continued change in solubility character, i. e., it seemed to be even less wa ter-soluble or dispersible than before, but was soluble in a mixture of 50% xylene and 50% non-aromatic kerosene. The product itself, on a Xylenefree basis, represented 25% sulfonate and 75% propylene oxide. On a xylene-containing basis, it represented 20% sulfonate, 20% xylene and 50% propylene oxide.

Example 22 A further addition of propylene oxide was made to the above reaction mass. The amount added was 300 grams. No more catalyst was added. The temperature and pressure ranges were within the same limits as in Example 21, preceding. The time required was approximately the same, to wit, 7 /2 hours. The product, on a xylene-free basis, was still water-dispersible to a degree and did not resented 20% sulfonate and 80% propylene oxide. On 7 a xylene-containing basis it represented 16.6% sulfonate, 66.8% propylene oxide, and 16.6% xylene.

Example 23 The same procedure was followed for all practical purposes, as in the four preceding examples, with the addition of another 300 grams of propylene oxide, along with 8 grams of sodium methylate. Thetime, temperature range, and pressure range were substantially the same as in thepreceding examples; to wit, time of 12% hours maximum, and a pressure of 190 pounds maximum. At the end of this addition of propylene oxide the product, on a xylene-free basis, represented one-sixth sulfonate and five-sixths propylene oxide. The product was soluble in approximately a fifty-fiftymixture of non-aromatic kerosene and xylene and showed even less solubility in water than the previous example.

1 Example 24 Without the addition of any more catalyst, the above reaction was given final treatment with another 300 grams of propylene oxide. The final product, on a xylene-free basis, represented one-seventh sulfonate and six-sevenths propylene oxide. The product was soluble in a mixture oftwo-thirds non-aromatic kerosene and one-third xylene. When freed from the small amount of xylene present and shaken up with water, it gave a cloudy suspension which tended to oil out of solution, showing extremely limited hydrophile properties. The temperature and pressure range was approximately the same as in the last three examples, preceding. The time period was the longest in the seriesbeing 16 hours.

In the above calculation and in previous calculations, no cognizance was taken of the presence of sodium methylate, except as far as weight percentages were concerned, and no cognizance was taken of the fact that small samples of 2 or 3 grams were taken out at the end of intermediate oxypropylations for examination.

As pointed out, this product dissolved in a mixture of two-thirds non-aromatic kerosene and one-third xylene, proved to be a particularly valuable agent in the preparation of emulsions, where the emulsifying agent was the original sulfonate itself. It was soluble to the extent of 1% or 2%, and probably to a greater degree in some typical lubricating oils which contained approximately to of additives. The bulk of these additives were alkaline earth soaps, mahogany sulfonates, or similar materials.

Example Grams Sulfonate, as described in Example 19 300 Xylene 300 Sodium methylate 17.5 Propylene oxide 1,800

Example 26 Grams Triamylated phenylphenol disulfonic acid sodium salt 300 Xylene 300 Sodium methylate 17.5 Propylene oxide 1,200

The procedure followed was the same as that described in Example 25, preceding, and the solubility characteristics of the final product were substantially the same as in the preceding example.

Example 27 Grams Trihexylated phenylphenol disulfonic acid sodium salt 300 Xylene 300 Sodium methylate 17.5 Propylene oxide 1,200

The procedure followed was the same as that described in Example 25, preceding, and the solubility characteristics of the final product were substantially the same as in the preceding sample.

.6 Example 28 Grams Trioctylated phenylphenol disulfonic acid sodium salt 300 Xylene 300 Sodium methylate 17.5 Propylene oxide 1,200

The procedure was the same as that described in Example 25, preceding. The solubility characteristics of the final product were substantially the same as in the preceding example.

Example 29 Grams Tridecylated phenylphenol disulfonic acid sodium salt 300 Xylene 300 Sodium methylate 17.5 Propylene oxide 1,200

The procedure followed was the same as that described in Example 25, preceding. The solubility characteristics of the final product were substantially the same as in the preceding example.

Example 30 Grams Monobutyl phenylphenol sodium monosulfonate 320 Propylene carbonate 2,640 Potassium carbonate 45 The powdered sulfonate, together with other reactants, was placed in a glass flask and heated to approximately C. and kept at this temperature for hours. The temperature was then raised to C. and held at this higher temperature for 8 hours. At the end of this period of time the weight indicated a loss of all the CO originally present in the propylene carbonate. The residual oxypropylated material was water-insoluble but soluble in hydrocarbon solvents, particularly xylene or a mixture of half xylene and half kerosene.

Example 31 Example 32 The procedure outlined in Example 31, preceding, was repeated except that 700 grams of butylene oxide (mixed isomers) was substituted for the 560 grams of propylene oxide employed in the preceding example.

' Example 33 The procedure of Example 30 was repeated employing 432 grams of dibutylated phenylphenol disulfonic acid sodium salt instead of 320 grams of monobutylated phenylphenol monosulfonic sodium salt as in Example 30, preceding.

Example 34 The Example 33 preceding is repeated except that the product was reacted further with propylene oxide in the same manner as described in Example 31, preceding.

Example 35 The same. procedure was followed as in Example 32, preceding, except that the product subjected to reaction with butylene oxide is the product derived by the proamass-'4 1 7 cedure outlined in Example 33 instead of Example 30, preceding.

Example 38 The same procedure'was' employed as in Example 32,

E l 36 precedingexcept that the reaction mass subjected to V 7 oxybutylation was the one descnbed under Example 3d, The same procedure was followed as in" Example 30 g g Instead of the descnbed" m Example a rece y preqedmg except thatflw sulfonatepmplgyed Ye P .1t is't o benoted that if propylene oxide is replaced 1x21112111; completely by me f me, were i1 s Patent 2166136 371 grams of sulfonate (sodiff decrease fr t g g g c ara r a er- 'e a n r r um salt) was used Instead of the 320 grams of the partici i' z g gg g i ii gz i g p g g; i u I a V 1 V a s ulzcllr sulfonatt; employed. In all other respectstheprorule if Propylene oxide we replaced memly weight for Ce um was e Same 1 Weight by butylene oxide, or partially replaced by butyfi l 37 lane oxide. All that is requiredis conformity to the xamp e minimum of fifteen moles of oxide as specified inprevions I descriptions. l 1. p I The same procedure was employed in all respects as In connection with a series of typiealoxyalkylatiqns described in Example 31, preceding; except that the reacmvolvrng primarily phenol sulfomc and salts WhlCh aI-e'- tion' mass subjected to further reaction with propylene readily ayallable, or can be readily prepared,anjclp'art1ciioxide was the one described under Example 35, precedlarly derivatlves of alkylated phenyl phenols, somesolu ing, instead of the one described in'Example 30, precedb111ty-datahas been tabulated for convemence; In order ing. to emphasize the novelfe'atures'of the" present invention.

' 'mnnni,

7 Water solubility I Xylenesolubfllty Sultanate I used as Molar 7 Na salt ratio of a 2 2 15- 1 -20 1-5 2 2 15 20 V 15 Ex." isone added, moles moles moles oles moles moles "molesmoles .moles; mole's N0. shownas EtOif .PrO' BuO PrO PrO BuO PrO BuO .PtO PIO B110 starting any per per per per per per per per per per mtLin mole mole, mole ,mole mole mole mole mole mole .Imole Ex. No. sulfosulfo sulfosuliosulfosulfo sulfosulfo sultosulfo- 'nate n'ate' nate nate' nate nate natenate nate n'ate 1A.. '1' None s s D I I I I 1)" s s; 2A-- 5 None I S; S D I I I I3 D St 3 6 I s s a 1 1 a i t a s s 41L- 7 1 an 10' N33: s so D I I I I D. S '5: 6A.. 19 None s, s r s D D I I D s s 711-- 26' None s s I s 1) D I I D s 5- 8A.. 27- None 5 s s s 1) D I 1 'I 1); s s 9A.. 28 None si s S D D I a I; D s 5, 10A. 29 None s s s D' 1) I I D s s' 11A- 1 1:1 I B s s D D IQ A I Iv s; s 12A- 5 1:1 5 s s D D 1 I- I s s 13A- 6 1 1:1 I s s s D D I I I I ss" HA- 7 1:1 ss s D D I I I is: s

D=somewhat dispersibl or di separates out-rapidly on standine spersible, generally havingpresent considerable insoluble materlal whloh I=inso1uble; that is, dispersible only while shaking but separates almost completely when agitation stops.

TABLE II 1 Gms. V solved 2 I V Ex.No. Monosulionica'cldn'om sulfomc ormixed Neutrallz'adwlth- 'Gms Lot" acid with I base" e xylene 1C 24 612111 1 hen01m0l.wt.314... 500 500 28% NH4OH 91 2C do y p 500 500' NaOH invsgm. H10- 3G dn 500 500 TEA 237 4C--- d V 151 O 62' gms; H20. 10. 7 do 400 400 TEA. 151 do 400 400 Triethylanline; 103

TEiktrlethanolamlne.

TABLE III Water solubility Xylene solubility Sulfonate used as Molar Na salt ratio of 2 2 15 2 2 15 20 15 Ex. is one added moles moles moles moles moles moles moles moles moles moles No. shown as EtO if PrO BuO PrO PrO BuO PrO BuO PrO PrO BuO starting any pet per per per per per per per per per mtl. in mole mole mole mole mole mole mole mole mole mole Ex. N o. sultosullosulfosulfosuliosullosulfosulfosultosull'onate nate uate nate nato nate nate nato nate nate None S S S I I I I I S S None S S S I I I I I S S None S S S D D I I I D D None S S S D D I I I D D None S S S I I I I I S S None S S S I I I I I S S None S S S D D I I I D D None S S S D D I I I D D None S S S I I I I I S S None S S S I I I I I S S None 8 S S D D I I. I D a D None S S S D D I I I D D None S S S I I I I I S 8 None S S S I I I I I V S S None S S S D D I I I D D None S S S D D I I I D D For explanation of S, D, and I, see Table I.

Elsewhere it has been pointed out that when a product such as a phenol sulfonic acid salt as herein described is reacted with 15 moles or 20 moles of an oxidesuch as propylene oxide or butylene oxide, one does not obtain a product having exclusively 15 or 20 moles but, for example, in the latter case, obtains a cogeneric mixture, the bulk of which may have 20 moles of oxide or approximately 20 moles, yet some of the members of the mixture may have as few as 15 moles or less and sometimes as .many as or more.

Obviously, in the lower boundaries one obtains mixtures, part of which are water-soluble and part waterinsoluble. Note what is said at the bottom of Tablel in.

explaining such properties.

One can mix such cogeneric mixture with 1 to S-tirnes its weight of water at ordinary temperatures and allow a separation to take place within a few hours or to 24 hours. The insoluble layer can be withdrawn as meeting the specified characteristics. The aqueous layer can be withdrawn, water eliminated in the conventional manner by spray drying or vacuum distillation, and the residual product again subjected to further treatment with propylene oxide or butylene oxide :as required.

The layer which separates, although being water-insoluble, may contain some dissolved water. Such material can be rendered anhydrous in the usual manner, i. e., spray drying, vacuum distillation or using a phase-separating trap along with a water-insoluble solvent such as xylene. Also, it is obvious that the presence of an inert solvent used as a suspending agent such as xylene, of course, may affect water solubility 'in so far as the layer which separates out might represent a mixture of the oxyalkylated derivative plusxylene. If need be, the xylene may be eliminated by evaporation or vacuum distillation and then the solubility separation noted above be employed in connection with the solvent-free material.

For manypurposes, mixtures obtained which contain both water-soluble members and water-insoluble membei's have special utility in the preparation of emulsions or as additives in the preparation of emulsions. V

In light of what is said elsewhere in regard to the amine salts and also in light of the limits included in the claims, it is obvious that in many cases it is desirable to prepare not only amine salts but also sodium salts as exenipli- For many purposes, the sodium salt is suitable and most economical to prepare. However, as far as the sulfonic acid is concerned, it may be in combination with various cations, as hereinafter described. For the sake of simplicity, the invention will be described primarily from the standpoint of a sodium or potassium salt, par- .ticularly the former.

Regardless of what the cation happens to be, however, the sulfonic acid, prior to oxypropylation or oxybutylation, must be characterized by the fact that the sodium salt is usually xylene-insoluble, and that after oxypropylation or oxybutylation, the sodium salt may be soluble in ..keroseneor a mixture of xylene and kerosene. Butylene oxide is apt to render the sodium salt xylene-soluble.

In an important and restricted sense the present invention is concerned with treating a water-soluble, often xylene-insoluble sodium salt of a substituted phenol-sulfonic acid with propylene oxide or butylene oxide so as to reduce greatly its water-solubility and make the resultant compound, or compounds, soluble in xylene or comparable hydrocarbon solvents. Such xylene-soluble salts, and particularly the sodium salts, are valuable as additives in the preparation of emulsions. Extremely dilute emulsions, for instance, those in which the dispersed phase isless than two-tenths of a percent, and usually less thanone-tenthfof a percent, have been prepared without using an emulsifying agent. The majority of emulsions, however, are prepared by the use of an emulsifying agent, and thus, the emulsion system consists essentially of three ingredients. However, many technical emulsions actually have a fourth ingredient, which may 'be an emulsifier ofindifferent or interior effect, but is valuable, because it is a coupling agent or mutual solvent.

-See The Composition and Structure of Technical Emulsions, J. H. Goodey, Royal Australian Chem. J. and Proc., 16, 1949, pp. 47-75.

Another use forv the products herein described is an additive for lubricating oils, particularly petroleum lubricating oils, to give added detersive qualities, and hence,

group, can be reacted with various reagents, such as acids, imines, alkylene oxides other than propylene oxide, 7 and the like, to glVSlfllI'IhfiI' derivatives of distinct value.

tied by Tables I and III. In such instances, the solubility oxide (phenyl ethylene oxide), one obtains extremely When treated with one mole or several moles of styrene valuable additives for various lubricating oils. There are "'"availablefa large number of phenols which can be con- "v ted into sulfonic acids, and then into the corresponding sodium salt. As previously indicated, the particular one-selected as a starting material for the present purpose is one which is completely water-soluble in dilute solutagsasgs a4 substituted phenols,- etc.

The selection of phenol or phenol sulfon-ate, as such,

'is perfectly simple. The sodiumsalt, and usually a monosulfonate, freed from inorganic salts, if present, and from any other extraneous material, is :simply examinedtosee if it is water-soluble so as togive a 1% to5% solution in water at ordinary temperature,approximately C. A dilute solution, for example, .I% to 1%,:is exammm to see that it is surfaceeact'ive in 'the usual sense, i. e.,

:foams, emulsifies, lowers surface :'tension of water, etc,

under the same conditions as it'is examined for xylenesolubility. Preferably, the xylene-solubility should ?be practically nil (less than 3 to percent) at ordinary temperature. Such simple test will "readily indicateif it iszperfectlysuitable foruse in preparing the herein described oxypropylated or oxybutylated derivatives. xylene-soluble one may proceed, or if desired ethylene oxide orglycide .may be employed, to decrease xylene solubility or increase water solubility.orincreaseysurfaceactive properties.

The product is then subjected'to 'oxypropylation or oxybutylation, usingan amount not propylene oxide or butylene oxide at least equal to one third or two-thirds .mole of propyleneoxide or butylene 'oxide for. each-car- :bon atom present inthe phenol, sulfonate. If this amount .of propyleneoxide or' butylene oxide. doesnot give water insolubility, theprocessis continued until the amo'untof propylene oxide or butylene oxide added in molar amount is twice or :three times the number .of carbon atoms: present in the phenol sulfonate. .If, at this stage the resultant; product is not water-insoluble,more'can be employed. In any event, if 60 moles of butylene oxide per phenolic hydroxyl does produce water insolubility, it is .considered unsatisfactory for the reason that prohibitive amounts of propylene oxideior butylene oxide would be required. Suitable phenolshave been previously indicated, and include, among others, diamylphenol, monophenol, and particularly phenylphenols, which are most suitably obtained by the alkylation of orthohydroxydiphenyl with a suitablealcohol under conditions so as to yielda monosulfonate. .As alkylating agents thevarious aliphatic alcohols, as, for example, primary, secondary, or tertiary butyl alcohols, with straight or branched chain, such as n=butyl alcohol, methyl ethyl carbinol, trimethyl carbinol, 'n-amyl alcohol, isoamyl alcohohpropyl alcohol, ethyl alcohol, .octyl alcohol, decyl alcohol, and thelike, may be brought intoactionon theinitial material, and they maybe employed as-such, or in the form of their esters, such as the alkyl sulfates.

In light of the variety ofphenol sulfonates that may b employed, it is obvious that, in a general way, as the number of carbon atoms in the substituent group "or groups goes up, less propylene oxide or butylene oxide will be required, everything considered, to yield xylene solubility. Initially, however, the product must be watersoluble and surface active, at least aftertreatment with ethylene oxide .or the like as noted. This. means that in the rule suggested previously, the lower amount of propylene oxide or butylene oxide isapt to be used inconnection with the sulfonates of the higher or highestmolec- -ular weights, i. e., largest number'of carbon atoms in the lubricating oils :obtained from the usual petroleum sources. .lnsofarithat it is only-required that the product oriproducts show xylene-solubility and not necessarily kerosene-solubility, this statement may be something of an incongruity. Actually, however, even though the oxypropylationor' oxybutylation products do not show kerosene-solubility but. only'xylene-solubility, yet they can be addedto the synthetic polyoxyalkylene lubricants, and

also .to the conventionallubricates, due to the presence ofvarious polarand semi-polar additives, which are customarilyadded. Of course, if oxyalkylation yields kerosene-soluble. products, they may be more suitable for use 'as lubricant additives.

There areavailable a number of petroleum distillates whicharein the samedistillation range as kerosene, but due to theirsaromatic character, are not entirely satisfactory, income-instances, for purposes for vwhich kerosene is used. Such materials are sometimes referred to as kerosene-range distillates, or kerosene-range solvents. Insofarthat muchkerosene ordinarily produced is used for 3a .solvent, ratherthan for combustion or illumination,

noLdifEerentiationis .made in the present description, for reasonsxwhich are obvious.

Reference to kerosene-solubility means solubility in a non-aromatic kerosene or similarhigherboiling solvent.

As has been pointed out previously,'the potassium salts cen "be used as well as the'sodium salts, but have no particular advantage, except perhaps, somewhat greater's'olu- :bility. in xylene and non-polar hydrocarbon solvents.

Actually, having obtainedthe sodium salt, or, for-that matter, the potassium salt, one can also prepare other salts .from ,thefree acid which might not necessarily be satisfactory for oxypropylation or oxybutylation, in that the cation would contain a group susceptible to oxypropylation or oxybutylation as is the case in cyclohexylamine, monoethanolamine, diethanolamine, 'triethanol amine, morpholine, and high molal amines, as, for example, thezamines obtainedfrom higher fatty acids. Such salts may vary in water-solubility. Some of those mentioned are. just barely water-soluble, or fairly emulsifiable, as a rule.

The water solubility of certain amine salts may be less than the corresponding sodium or potassium salt. Similarly, the water solubility may be greater than the corresponding sodium or potassium salts. Reference to water solubility is an approximate term intended to indicate in a general way the amount of propylene oxide or butylene oxide required to convert to Water, insolubility. Regardless of the solubility characteristics of the amine salts, whether tending 'to increase the hydrophobe effect or the hydrophile effect, it is still necessary thatthe'corresponding sodium salt show the solubilities specified. As pointed out elsewhere, there is no reasonwhy one may not use an amine salt and subject it to treatment with propylene oxide or butylene oxide, notwithstanding the fact that the salt may be susceptible to oxyalkylation in the amine radical position provided, however, that the corresponding sodium salt still meets the requirement and that there is the degree of oxyalkylation employin'g either propylene oxide or butylene oxide tomeet the herein stated'requirement.

Acidification of the sodium or potassium salts yields a correspondingly free acid of the following composition (or the equivalent):

Such materials which are thrown out'by hydrochloric acid can be purified in the conventional manner "by evaporation, so as to eliminate the inorganicimpurities and the acid and can then be neutralized 'withanyconvenient base, such as those-above enumerated, or with ammonia, tertiary amines, or can be converted into the salts of other metals, such as lithium, calcium, magnesium, strontium, barium, etc. The ammonia and amine salts, particularly when derived from water-soluble amines, have utility as coupling agents in the same manner as previously described. In fact, the salts derived from triethanolamine have unusual value as coupling agents. Those derived from high molal amines show increased oil-solubility over and above the sodium salt, as in the case of the cyclohexylamine salt. These salts are particularly valuable lubricant additives. The copper salt is a valuable additive for materials employed to prevent or repel certain types of insect 'or microorganic ravage. a

In obtaining the free acid from the sodium salt or a potassium salt, if it happened to be employed, it is usually desirable to eliminate the xylene or other solvent prior to acidification. In some instances, the higher oxypropylated or oxybutylated derivatives seem to be slightly heavier than waterand may separate at the bottom instead of rising to the top. In some instances, this is purely a question of how much acid is added. In other words, if the specific gravity of the aqueous hydrochloric acid solution is sufiiciently high, the product separates at the top; otherwise, it may separate at'the bottom. Since the free acid is frequently xylene-soluble, if xylene or some other solvent is present, then and in that event, of course, it affects the specific gravity of the non-aqueous phase, and thus, again may be a factor in determining whether a supernatant layer comes out at the top, or an oily layer saparates, at the bottom. The objection to the use of a salt as a source of the selected cation is only that at least partial neutralization of the sulfonic acid may take place. Needless to say, if one intended to prepare the ammonium salt, ammonium chloride could be used to hasten the separation. Similarly, if the triethanolamine salt is to be formed, triethanolamine hydrochloride (triethanol ammonium chloride) could be employed.

Reference is now made to a number of previous formulae, in which the divalent radical -(C H O),, appears. One example is R SOa.X

Actually, when such products are obtained in the manner herein described, one does not obtain a single derivative, in which n has one and only one value, for instance, 14 or 15 or 16, or the like. Actually, one obtains a cogeneric mixture of closely related or touching homologues. These materials invariably have high molecular weights and cannot be separated from one another by,

any known procedure without decomposition. The properties of such mixture represent the contribution of the various individual members of the mixture. On a statistical basis, of course, n can be appropriately specified. For practical purposes, one need only consider the oxypropylation of a monohydric alcohol, because, in essence, this is substantially the mechanism involved. Even in such instances where one is concerned with a monohydric reactant, one cannot draw a single formula and say that, by following such procedure, one can readily obtain 80% or 90% or 100% of such compound. However, in the case of at least monohydric initial reactants, one can readily draw the formulae'of a large number of compounds which appear in some of the probable mixtures, or can be prepared as components and mixtures which are manufactured conventionally.

Simply by way of illustration, reference is made to U. S. Patent 2,549,434 dated April 17, 1951 to De Groote, Wirtel, and Pettingill.

H However, momentarily referring again to a monohydric initial reactant, it is :obvious that if one selects any such simple hydroxylated compound and subjects such compound to oxyalkylation, such as oxyethylation, oxypropylation, or oxybutylation, it becomes obvious that one is really producing a polymer of the alkylene oxide, except for the terminal group. This is particularly true where the amount of oxide added is comparatively large, for instance, 10, 20, 30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce 30 units of ethylene oxide, it is well known that one does not obtain a single constituent, which, for the sake of convenience,rmay be indicated as RO(C H O) OH. Instead, one obtains a cogeneric mixture of closely related homolo'gues, in which the formula may be shown as the following: RO(C H O),,H, wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25, and perhaps less, to a point where n may represent 35 or more. Such mixture is, as stated, a cogeneric closely related series of touching homologous compounds. Considerable investigation has been made in regard to the distribution curves for linear polymers. Attention is directed to the article entitled Fundamental Principles of Condensation Polymerization, by Paul I. Flory, which appeared in Chemical Reviews, volume 39, No. 1, page 137.

Unfortunately, as has been pointed out by Flory and other'investigators, there is no satisfactory method, based on' either experimental or mathematical examination, of indicating the exact proportion of the various members of touching homologous series which appear in cogeneric condensation products of the kind described. This means that from the practical standpoint, i. e., the ability to describe how to make the product under consideration and how to repeat such production time after time without difficulty, it is necessary to resort to some other method of description, or else consider the value of n in a formula such as I a tO)n g SOa.X

as representing both individual constituents, in which n has a single definitive value, and also with the understanding that n represents the average value, based on completeness of reaction.

This may be illustrated as follows: Assume that in any particular example the molal ratio of the propylene oxide or butylene oxide to the sulfonate is 15 to 1. Actually, one obtains products, in which n probably varies from 10 to 20, perhaps even further. The average value, however, is 15, assuming, as previously stated, that the reaction is complete. The product described by the formula may be described also in terms of method of manufacture, but insofar that a single hydroxyl only is involved, as diiferentiated from materials obtained by oxypropylation or oxybutylati'on of p'olyhydric reactants, it appears more satisfactory to employ the customary formula type description, as long as the obvious limitations are completely understood.

A similar procedure can be employed in connection with phenol sulfonic acids which are amine neutralized or neutralized by means of quaternary ammonium bases such as tetraethanol ammonium hydroxide. The difliculty in the case of the quaternary ammonium bases is that there is a tendency to decompose under conditions of oxypropylation or oxybutylation. In any event, any amine employed, whether primary, secondary or tertiary amine or whether it contains a hydroxyl group or not as in the case of triamine, involves a cation or radical which is oxyalkylation-susceptible. Also, the cation as such may influence the solubility prior to oxypropylation or oxybutylation and also after oxy-propylation or oxybutylation.

25 "For instance,cthe' triethanolamirie --salts of sulfonic acids frequently-show greater water solubility or, stated another way,tlesser, indi'catedxylehe solubility than the comparable sodiumsa'lt. This elfectmay tend to reverse if tripro- "panolainine or tributanolamine is employed; 'The effect is also reversed, of course, ifthe hydi'ophobe amine such as dodecylamine is employed. a

On the other hand, oxyalkylation may be affected by steric factors which vary with individual examples. Neutralization, for example, with triethylamine yields a cation having a labile hydrogen susceptible to oxypropylation or oxybutylation. Actual experience, for example, with tri-ethylamine, seems to indicate that very little, if any, oxypropylation or oxybu'tylation takes place under usual conditions. Thus, without any variation, any amine salt can be used provided, (1) the solubility characteristics before and after. oxypropylation are not changed and, (2) no appreciable oxypropylation takes place at the anion. Actually the amine'radical may be oxyalkylationsusoeptible provided that certain limitations are met as described subsequently. y y y The amine salts are included in the final product for .the reasonthatthey can be obtained by previous sug- ,ges ted procedure, i. e., liberating the free acid by .con-

ventional neutralization. Thus, having obtained the free acids they. may be neutralized with monoethylamine, diethylamino; triethylamine, tetraethylamine,'tributylamine, diethylaminoethanol, dimethylaminoet-hanol, dibutylami- .noethanol, ethylamine, n-propylamine, isopropylamine, nbutylarnine, sec-butylamine, isobutylamine, 1,3-dimethylbutylamine, triamylamine, and N,N- diethylcyc1ohexylamine, Needless to say, ammonium hydroxide can be employed, I

The amine salts whichmay beobtained, inthe manner preyiously indicated are valuable for certain purposes .where sodium or potassium salt isless satisfactory. The purposes are illustrated by theinuse as an additivetofue] oil to -preventtl) corrosion, (2) separation of solidamat- -,ter, and (3) holdanymoistureinsolutionorsuspension. whenfuel oil 3 is burnedy-and the same forthat matter would apply to heavy combustiome'n-gines,there isaan lash deposit which .clogs the burner or ,causes equivalent ,ptechanical difiiculties. The presence of ansodium or -potassiu masalt increases such deposits. ,Thus, the useof an amine, salt is indicated. Suitableaminesalts include not nl-ythose previously described but also those obtained from polyaminessuch as ethylenediamine, diethylenetriamine, triethylenetetramine, etc. as well as cycloamidi'nes such as 1 I] W :1 C "Her-C- v CH3 For this. reason the freeacids .as such prior to neutraliza- "ti-on resent an inherent "part of the present invention. Ne l s. to say, if a polyamine is usedhaving two tions. Suchcations include sodium, potassium, A

of the corresponding oxides, although having other 'advantages as indicated. .For purpose of clarity of presentation, reference "in the c'la'irnsto an oxyalkylating agent selected from a class consisting or p-rbp iene oxide and butylene oxide or a. mixture 'of the two obviously includes the carbonates or mixtures of carbonates just as well. iT-hessamek'appliesrto ethylene :carbdhate. The-two iclasses ofareagents are more than the. obvious :chemic'al lequivalentsheing, inifact-andin reality,itwo.tfotms ofthe same oxyalkylating agent.

It is understood that onecan start with a salt form which includes inthe-cationic group which is in turn an alkylation-susceptible radical, foi instance, a suitable sulfonic acid neutralized with triethanolamine. However, under such circumstances :oxyalkylation must take place at the hydfoxylposition at least to a degree suf- ;ficient that the ,sulfonic acid radicalmeets the :requirement previously :indicated and that the corresponding sodiumgsalt is water-insoluble. During-such oxyalkyla- .tion v reaction may ,alsotake place atthecation. and thus at the-endof oxyalkylation theradicalis changed to the ext entth at it;would.-re'present an oxyalky'lated triethanolamine. Needless to; say-,-in order to determine; such dis- -tribution,..-all that is necessary is :to split the acid with concentrated causticsodaor the like seas to liberate the amine or'oxyalkylatedamin'e and determine its composition,-;particularly ,the,nitrogen content and molecular weight. .Insome r:ases,;it is preferableto just split with astrong 1acid'-.such as=HC1. Similarly, .the sodium salt in which 'R-is an ald llyderesidii and an' l represents "an alkyl radical which may contain from; to '8 carbon *ator'ns'anld eve'ii'inore as i'n thecase er uinony p enol,

didecyl phenol, di'tettadecyl pheno1 etc.. such pheno s have been described in various patent and particularly "U. s. Patentzamamaaaiea my 27, ta is-tone "G age et :11. "Such phenols, when vert'tl into ap r ate "aoids "or salts; illustrates the type'where there are four alkyl substituents. k

However, the instant inv ntion is net intended to include soivene-samble-phenalresins of'th'e obtained from a difunctional phenol and formaldehyde or an equiv- 1 .alent aldehyde having "generally-eight carbon atoms or "less. Such soluble resinshave been described in a number of UJ S. patents, an psrt eular y as U. s. Patents 2;499,365, 2,'499;3'66', 2,499;36 7,'2;4 99,368 616., all dated March 7, '19'50, to De Gi'oo te et a1. 7 Such resin 'are sometimes described in an bver=s'itnplifi'ed "formula .as

follows in which n represents a numeral varying from -1 to 13 and R is}: substituent, generally a hydrocarbon substituent having'f'rorn 4 to 18 .carbon atoms and may vary from l to 2 4 The "formaldehyde nucleus, of course,.rnay be replaced by a radical derived .from some other aldehyde. Such resins, as f distinguishe'd from phenols, vcan be'di'ssolved in a suitable solvent such as dioxane, a substituted 'dioxan'e, or any otherfsuitable solvents. Such resins in solution can be reacted with anhydrous sulfur trimmers the conventional manner so as to introduce one-6r-msresu1fonic acid radicals. In numerous e5:- ampies whefe thefvalue of nJhaS been 1, 2, '3 or '4, and generally -1 oi' 2, tife i'esfii has-bee'n reacted with either .one mole of sulfur trioxide or two or more moles of sulfur trioxide and the sulfonic acid obtained may be indicated thus 7 in which n is 1 and n" is or 1. The acids can be neutralized in a conventional manner using the same procedure as described above in respect to the instant invention. The added solvent may be allowed to remain or can be eliminated by extraction or distillation, particularly vacuum distillation. Water can be eliminated in the usual manner involving either vacuum distillation or the use of a water-insoluble solvent with a phase-separating trap. The solvent-free anhydrous salt can be redissolved, if desired, in a non-oxyalkylation-susceptible solvent such as xylene, cymene, tetralin, high-boiling aromatic naphtha, etc. Such sulfonic acids and, for that matter, their salts such as sodium, potassium, ammonium, diethanolamine salt, triethanolamine salt, etc., would vary all through the solubility range. Specifically, this applies to comparable compounds, thus,

in which X represents a cation which may be hydrogen or may be any one of the metals previously referred to or any one of the amines previously referred to whether oxyalkylation-susceptible or not and either monoamino or polyamino. Needless to say, where X represents a cation having a valency greater than 1, as in the case of a polyamine or in the case of a metal such as zinc, cop per, aluminum, etc., the structure becomes more com plicated but will be ignored for the present which is only for the purpose of establishing a line of demarkation. However, it is to be noted that the solubility of such compounds depends on factors such as (l) the size of the .substituent R, (2) the size of the aldehyde radical, (3) the number of units in the resin molecule, i. e., the value of n, (4) the character-of the cation X, and (5) the number of sulfonic acid radicals introduced, etc.

, Such products may be water-soluble and completely insoluble in xylene or non-aromatic kerosene. Inversely, such products may be completely soluble in non-aromatic kerosene and xylene and absolutely insoluble in water. Whatever the initial characteristics of such products, they may be subjected to oxyalkylation in the manner herein described, both by means of the alkylene oxides and the alkylene carbonates. Oxyalkylation may completely vary the solubility characteristics and surface-active characteristics of the initial products. Reaction may take place at the hydroxyl position only or both at the hydroxyl and the cationic position as previously pointed out in regard to the instant invention. The use of ethylene oxide, glycide, and, to a lesser extent, methyl glycide increases the water solubility properties and decreases solubility in hydrophobe solvents. Inversely, propylene oxide and butylene oxide decreases solubility in hydrophile solvents and increases solubility in hydrophobe solvents. The amount of oxides or carbonates used may represent a 2 to l, 5 to 1, ml, 20 to 1, or even 50 to 1 ratio, based on the initial sulfonate. One need not use a single oxide or carbonate but can use a mixture. The products so obtained are useful not only for all the purposes herein enumerated in connection with the present invention but are also useful for a variety of other purposes where surface-active agents serve as, for example, such products can he used for the resolution of petroleum emulsions oi 'hydroxyl radical.

operations using aqueous fioodwaters. also are suitable for use in dry cleaners soaps.

the water-'in-oil type as described in Part 3 of U. S. Patent 2,626,926, dated January 27, 1953, to De Groote. Furthermore, such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine, one may employ what is a somewhate equivalent material, to

wit, a dialkylaminoepoxypropane of the structure wherein R and R" are alkyl groups.

Furthermore, such products, in addition to their use in the resolution of petroleum emulsions, may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and wetting agents in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud "sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery These derivatives And, furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-in-water emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A water-insoluble salt of the following composition:

Cation (SO3)m(R')n(R) in which R is' an aryl nucleus; R' is a hydrocarbon substituent having not over 22 carbon atoms with the proviso that the combined radical (R'),,R contains not over 2 aryl rings; R 0 is an alkylenoxy radical derived from a member of the class consisting of ethylene oxide, glycide, and methyl glycide; R 0 is an alkylenoxy radical derived from a member of the class consisting of propylene oxide and butylene oxide; m is a numeral from 1 to 2; n is a numeral from 1 to 4; n is a numeral from O to 5; n" is a numeral-homo to l; n is. a numeral from 15 to 60; 'n"f isa numeral from 1 to 6 butnot greater than the valence equivalency of the cationic portion of the molecule; said salt being a salt of the acid in which the characters have their previous significance.

2. A water-insoluble salt of the following composition:

in which R is an aryl nucleus; R is a hydrocarbon substituent having not over 22 carbon atoms with the proviso that the combined radical (R) ,R contains not over 2 aryl rings; R is an alkylenoxy radical derived from a member of the class consisting of ethylene oxide, glycide, and methyl glycide; R 0 is an alkylenoxy radical derived from a member of the class consisting of propylene oxide and butylene oxide; n is a numeral from 1 to 4; n is a numeral from 0 to 2; n" is a numeral from 0 to 5; n is a numeral from 15 to 60; n"" is a numeral from 1 to 6 but not greater than the valence equivalency of the cation; said salt being a salt of the acid in which the characters have their previous significance. 3. A water-insoluble salt of the following composition:

in which R is an aryl nucleus; R is a hydrocarbon substituent having not over 22 carbon atoms with the proviso that the combined radical (R),,R contains not over 2 aryl rings; R 0 is an alkylenoxy radical derived from a member of the class consisting of ethylene oxide, glycide, and methyl glycide; R 0 is an alkylenoxy radical derived from a member of the class consisting of propylene oxide and butylene oxide; n is a numeral from 1 to 4; n is a numeral from 0 to 5; n is a numeral from 15 to 60; said salt being a salt of the acid in which the characters have their previous significance.

4. The product defined in claim 3 with the proviso that the radical R be monocyclic.

5. The product of claim 3 with the proviso that the radical R be monocyclic and the total number of substituent carbon atoms in the combined radical (R),,R be not over 28 and that the combined radical (R'),,R represent an aliphatic substituted phenol radical.

6. The product of claim 1 with the proviso that at least part of the alkylenoxy radical R 0 be derived from butylene oxide.

7. The product of claim 2 with the proviso that at least part of the alkylenoxy radical R 0 be derived from butylene oxide.

8. The product of claim 3 with the proviso that at least part of the alkylenoxy radical R 0 be derived from butylene oxide.

9. The product of claim 4 with the proviso that at least part of the alkylenoxy radical R 0 be derived from butylene oxide.

10. The product of claim 5 with the proviso that at least part of the alkylenoxy radical R 0 be derived from butylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS 2,135,978 Magoun Nov. 8, 1938 2,143,759 Bruson et a1 I an. 10, 1939 2,166,136 Flett July 18, 1939 2,176,833 Bruson et al Oct. 17, 1939 2,184,935 Bruson et al Dec. 26, 1939 2,226,119 De Groote et al. Dec. 24, 1940 2,448,664 Fife et a1 May 30, 1944 2,552,528 De Groote May 15, 1951 2,615,853 Kirkpatrick et a1 Oct. 28, 1952 

1. A WATER-INSOLUBLE SALT OF THE FOLLOWING COMPOSITION: 